Microbiocidal fabric having phosphate derivatives and method of preparation thereof

ABSTRACT

The present invention relates to microbiocidal compositions and methods for the preparation and use of of such compositions. Properly used in accordance with the present invention, these microbiocidal compositions are effective in killing or inhibiting a wide variety of harmful, destructive or offensive microorganisms including viruses, bacteria, yeasts, algae and molds. The microbiocidal compositions of the present invention are suitable for use with conventional detergents to provide microbiocidal cleansing agents. The microbiocidal compositions can also be mixed with a liquid to provide an effective disinfectant. The microbiocidal additive can be incorporated into plastic materials and various synthetic fibers thereby imparting microbiocidal activity to the plastic materials or fibers. In addition, the microbiocidal compositions of the present invention can be incorporated into a wide variety of permanent and nonpermanent coating materials including, but not limited to, paints, varnishes, epoxy coatings and waxes. The microbiocidal compositions can also be used as a preservative for protecting wood and wood products from damage by microorganisms or insects. The microbiocidal compositions of the present invention can also be used to kill or repel insects.

CROSS-REFERENCE TO RELATED CASES

This is a divisional of application Ser. No. 07/047,561 filed on Apr.27, 1987, now allowed; which is a continuation-in-part of applicationSer. No. 781,710 filed on Oct. 2, 1985; 635,728 filed on July 30, 1984,now abandoned; application Ser. No. 658,695 filed on Oct. 9, 1984, nowabandoned; application Ser. No. 713,445 filed on Mar. 19, 1985, nowabandoned; application Ser. No. 736,652 filed on May 21, 1985;application Ser. No. 744,916 filed on June 13, 1985; and applicationSer. No. 744,730 filed on June 13, 1985, now abandoned; all of which arecontinuations-in-part of application Ser. No. 570,952 filed Mar. 8,1984, which in turn was a continuation of application Ser. No. 523,734filed Aug. 16, 1983, now abandoned, which was a continuation ofapplication Ser. No. 226,006 filed Jan. 19, 1981, now abandoned, whichwas a continuation of application Ser. No. 930,879 filed Aug. 4, 1978,also now abandoned.

TECHNICAL FIELD

The present invention relates to microbiocidal compositions and methodsfor the preparation and use of such compositions. Properly used inaccordance with the present invention, these microbiocidal compositionsare effective in killing or inhibiting a wide variety of harmful,destructive, or offensive microorganisms including viruses, bacteria,algae, yeasts, and molds.

BACKGROUND

Discussion of the present invention and its background will befacilitated by definition of several terms.

As used herein, the term "microorganism" means any organism that cannoteasily be seen with the naked eye and includes organisms such asbacteria, molds, yeasts, fungi, algae and viruses. "Antimicrobial" and"microbiocidal" describe the killing of, as well as the inhibition ofthe growth of, bacteria, yeasts, fungi, algae, and molds. "Bactericidal"describes the killing or inhibition of the growth of bacteria."Fungicidal" describes the killing of, as well as the inhibition of thegrowth of, fungi, yeasts and molds. The term "viricidal" is used todescribe the inactivation of virus particles so that they are unable toinfect host cells. The term "plastic," as used herein, includes boththermosetting and thermoplastic materials. Examples of "plastic"materials include, but are not limited to, polyolefins (such aspolyethylenes, polypropylenes, polybutylenes) polystyrenes, vinylphenolics, vinyl acetates, polymeric vinyl chlorides, ureas, melamines,acrylics, polyesters, epoxies and nylons. The term "molded" as used inthis application is used in its broad sense to include any technique forforming plastic or other materials. Molding is generally, but notalways, accomplished with elevated temperature and includes, but is notlimited to, forming methods such as potting, extruding, sheeting,calendering, pulltruding, casting, vacuum forming, blow molding, and thelike.

The term "cleansing agent" includes any substance capable of cleaning,emulsifying, or removing unwanted material from a surface. The term"detergent" describes any substance or product which is capable ofdislodging, removing, or dispersing solid and liquid soils from asurface being cleansed. The term "detergent" also includes soapscomprising metal salts of long chain fatty acids. The term"disinfectant" includes any liquid that is capable of killing orinhibiting microorganisms.

The term "free hydroxy" as used herein means an oxygen that is bonded toa phosphorus in a phosphate group.

Bacteria, fungi, viruses, algae and other microorganisms are alwayspresent in our environment. Such microorganisms are frequently anessential part of ecological systems, industrial processes, and healthyhuman and animal bodily functions, such as digestion. In otherinstances, however, the presence of microorganisms is highly undesirablebecause they may cause illnesses or death of humans and animals, createodors and damage or destroy a wide variety of materials.

The species and numbers of microorganisms present vary depending on thegeneral environment, on the nutrients and the moisture available for thegrowth of the microorganisms, and on humidity and temperature of thelocal environment. Nutrients for microorganisms abound in the normalenvironment. Any protein matter such as dried skin, discarded foods,plants, and animal wastes all are excellent nutrient media for manytypes of potentially harmful microorganisms. Furthermore, many organicsynthetic and natural materials like plastic coatings and objects, andwood, paper and natural fibers can serve as nutrients for microorganismswhich will degrade those materials. In addition, certain bacteria arecapable of remaining viable in a dormant state on floors or on objectsfor long periods of time until they are deposited in the proper mediafor growth. Consequently, potentially harmful microorganisms can betransported merely by walking on floors, brushing against walls orfurniture or by handling objects.

It is well recognized that a major difficulty in health care facilities,such as hospitals and nursing homes, is the spread of dangerousinfectious diseases caused by a wide variety of microorganisms. Theproblem is exacerbated in these facilities because many of the patientsare in a weakened condition due to their primary health care problem. Amicroorganism that would not be a major threat to a healthy person couldbe fatal to a patient with a diminished capacity to defend himself frominfection.

Potentially dangerous microorganisms are spread in health carefacilities and elsewhere by a variety of vectors. One of the most commonvectors is health care personnel. For example, a nurse or doctor mayadminister care to one patient and then be called upon to treat a secondpatient. Even though he or she may carefully wash his or her handsbefore treating the second patient, potentially dangerous microorganismsmay be transferred from the first patient to the second patient. Themicroorganism can then cause a serious infection in the second patient.

Furthermore, plastic products are often used in hospitals and otherhealth care facilities. These products are particularly susceptible tocontamination by bacteria and other harmful organisms. Conventionally,the plastic products in these facilities are periodically cleaned withstrong cleansers to remove or kill accumulated microorganisms. Betweenthese cleanings, however, it is possible for the plastic products toaccumulate a sufficient quantity or quality of bacteria or othermicroorganisms to constitute a major vector for cross-infection orspread of infectious diseases.

Pathogenic microorganisms can also be deposited on fabrics such astowels, clothes, laboratory coats and other fabrics. Thesemicroorganisms can remain viable on these fabrics for long periods oftime. If the fabrics are used by several different people, themicroorganisms can be transferred by people walking from one part of thefacility to another.

As mentioned above, the plastics that are used to make plastic objectsand coatings can themselves be a substrate for growth of variousmicroorganisms, such as bacteria, mold and mildew. The same is true forfibers and fabrics, some of which are plastics and other organicmaterials such as wood and paper. When these microorganisms grow on orin a plastic product, fiber, or fabric, they form unsightly colonies. Inaddition, such microorganisms can eventually break down a plastic,fiber, fabric, or other material. Plastic, fiber and fabric productsoften must therefore be frequently cleaned with a strong cleanser todestroy, or at least control, the growth of the microorganisms. A moreeffective approach to the problem is clearly needed.

Potentially destructive microorganisms also tend to collect and residein clothing and in fabrics regardless of whether they provide a nutrientsubstrate. Clothing that is used when exercising is particularlysusceptible to the accumulation of destructive microorganisms. If thesemicroorganisms are not killed or inhibited, they may cause extensivedamage to the fabric, not to mention causing offensive odors andinfections. Washing with conventional detergents does not always kill orremove many of these microorganisms. Thus, a microbiocidal additive isneeded that will kill or inhibit the microorganisms residing on thefabric and, at the same time, not cause deterioration of the fabric andnot cause adverse physical reactions in the individual that is wearingthe fabric.

In short, the control of microbial contamination and infection has beena major problem throughout history in both industry and the home, andsuch infection and contamination continues to cause disease, death, anddestruction of property. It has proved difficult, however, to develop amicrobiocidal additive that is effective in controlling the growth of awide variety of unwanted microorganisms and is, at the same time, safefor use around human beings and animals. Accordingly, there is an acuteneed, both in industry and in the home, for a safe and effectivemicrobiocidal additive that can be used in or on a wide variety ofsubstances to impart microbiocidal activity to the product from whichthe substance is made.

One of the sources of difficulty in the control of potentially harmfulmicroorganisms is the extreme variability of response of variousmicroorganisms to conventional microbiocidal agents. For example,bacteria, which are classified as procaryotes, can be killed orinhibited by many different types of antibiotics. However, these sameantibiotics that are effective against procaryotic organisms are usuallyineffective against eucaryotic microorganisms, such as fungi and yeasts.

Even within the family of Bacteriaceae, there are two broad categoriesof bacteria known as Gram-positive and Gram-negative bacteria. Theseclassifications stem from the ability or non-ability of bacteria toabsorb certain vital stains, and the two groups of bacteria generallyrespond differently to the same microbiocidal agent. A particular agentthat may be effective against one group may not be effective against theother group.

One conventional method of inhibiting the growth of both eucaryotes andprocaryotes or both Gram-negative and Gram-positive bacteria is tocombine two or more microbiocidal inhibitors, each designed to inhibitor kill a specific organism or class of organisms. However, variousproblems arise when introducing two or more additives into a materialsuch as a detergent. The multiple additive system may alter the physicalproperties of the detergent into which it is mixed. In addition, themultiple components must be tested to insure compatibility and continuedmicrobiocidal effectiveness when combined with the detergent. Therelative microbiocidal or microbiostatic strength of each of thecomponents in the multiple system must be determined. It is not uncommonfor the combination of microbiocidal additives to initially haveeffective inhibiting or killing properties for both Gram-positive andGram-negative organisms whereupon, with the passage of time, one or theother of the inhibiting additives will deteriorate and lose itseffectiveness while the other inhibiting additive remains effective. Inaddition, one additive may have an unexpected inhibitory effect on theother additive. In addition, the requirement of adding two or moreadditives can become prohibitively expensive.

The ideal microbiocidal additive must be non-toxic to humans and animalsaround which the additive is used. Such an additive should not cause anallergic reaction and must have no long term detrimental health effectson humans or animals. Finally, such an microbiocidal additive should becompatible with the material with which it is being used and not causethe material to deteriorate or lose its desired properties.

SUMMARY OF THE INVENTION

The present invention solves the problems described above by providing acomposition including a broad spectrum, safe, microbiocidal additivethat is effective in killing or inhibiting a wide variety ofmicroorganisms including viruses, bacteria, yeasts, molds and fungi andalgae. The microbiocidal additive comprises a phosphate derivativehaving microbiocidal activity. The microbiocidal phosphate derivativehas at least one free hydroxyl group thereon.

The microbiocidal additive of the present invention is a phosphatederivative with at least one free hydroxyl group. The phosphatederivative has the following general formula: ##STR1## wherein:

R may be alkyl, aryl, aralkyl and alkaryl groups including, but notlimited to, straight chain, branched chain or cyclic alkyl groups havingfrom 1 to 24 carbon atoms, polyoxyethylene or polyoxypropylene havingfrom 2 to 32 ethylene oxide or propylene oxide units respectively, alkylphenoxy polyoxyethylene containing 2 to 32 ethylene oxide units, alkylphenoxy polyoxyethylene containing ethylene oxide units and 1 to 24carbon atoms in the phenolic alkyl chain, and polyhydroxy compounds,including but not limited to, ethylene glycol, glycerol, or sorbitol.

X is selected from the group consisting of Group IA metals, Group IIAmetals, transition metals, hydrogen, and an organic ion. The positivelycharge ion is not necessary for microbiocidal activity.

The microbiocidal additive of the present invention can be added to awide variety of materials in accordance with the present invention toimpart microbiocidal activity to those materials.

For example, the microbiocidal additive of the present invention can beadded to aqueous solutions of detergents in accordance with the presentinvention to provide microbiocidal cleansing agents. In addition, thepresent invention can be added to water or other solvents to provide aneffective disinfectant.

Additionally, the microbiocidal additive of the present invention can beadded to both permanent and non-permanent coating materials inaccordance with the present invention. When the coating material isapplied to a surface, the microbiocidal additive that has been added tothe coating material will impart long lasting microbiocidal activity tothe surface.

Furthermore, the microbiocidal additive of the present invention canalso be incorporated into a wide variety of plastics in accordance withthe present invention to impart microbiocidal activity to the objectsmade from the plastics. When incorporated into the plastic material, themicrobiocidal additive of the present invention inhibits the growth ofmicroorganisms over a long period of time and protects the plastic fromdegradation by harmful microorganisms. In addition, the microbiocidaladditive utilized in accordance with the present invention does notchange the desirable properties of the plastic material.

The microbiocidal additive of the present invention can be appliedtopically to both natural and synthetic fibers in accordance with thepresent invention. The present invention can also be incorporateddirectly into synthetic fibers to impart microbiocidal activity to thefibers or to fabrics made from the fibers. In addition, themicrobiocidal additive of the present invention can be applied directlyto a fabric.

The microbiocidal additive of the present invention can also be added tocoatings that are designed to coat surfaces that remain for long periodsof time in water such as boat bottoms. Alternatively, the microbiocidaladditive of the present invention can be incorporated into a materialthat is designed to remain in water for long periods of time. A materialthat is treated with the microbiocidal additive of the present inventionwill inhibit the growth of algae on the surface of the treated material.

As a final illustration, the above described microbiocidal additive ofthe present invention can be applied to materials as a preservative. Forexample, the additive can be applied to wood and wood products toinhibit the deterioration of the product due to microbiocidal growth. Ithas been determined that the microbiocidal additive of the presentinvention is effective in inhibiting infestation of insects, such astermites, in wood and is therefore a good preservative against insectinfestation when applied to wood and wood products.

The microbiocidal additive utilized in practicing the present inventioncan also be mixed with liquids such as inks, fuels, and lubricating oilsto inhibit the growth of microorganisms. The microbiocidal additive ofthe present invention is capable of killing the causitive organism ofLegionaires' disease, Legionella pneumophilia. Thus, the presentinvention embraces addition of the identified compound to cooling towerwater to control the growth of this pathological organism.

Accordingly, it is an object of the present invention to provide for useof microbiocidally effective phosphate derivatives in and on a varietyof products.

Another object of the present invention is to provide for the use ofmicrobiocidally effective phosphate derivatives which can be added to anaqueous detergent to impart microbiocidal activity to the detergent.

Yet another object of the present invention is to provide for theaddition of microbiocidally effective phosphate derivatives to water orother solvents to provide effective disinfectants.

Another object of the present invention is to provide for addition ofmicrobiocidally effective phosphate derivatives to permanent andnon-permanent coatings.

Another object of the present invention is to provide for incorporationof microbiocidally effective phosphate derivatives into plastics toprovide a self-sanitizing plastic product with microbiocidal activityagainst a wide variety of organisms including bacteria, fungi, molds,algae and viruses.

Yet another object of the present invention is to provide forincorporation of microbiocidally effective phosphate derivatives intosynthetic fibers or fabrics to provide a selfsantizing fiber or fabricproduct with microbiocidal activity against a wide variety of organisms.

Another object of the present invention is to provide for incorporationof microbiocidally effective phosphate derivatives in objects andliquids to preserve the objects or liquids against degradation bymicroorganisms.

Another object of the present invention is to provide for incorportioninto products or application onto products of microbiocidally effectivephosphate derivatives to preserve the products from degradation bymicroorganisms.

Another object of the present invention is to provide a product that iseffective in retarding or killing insects.

Another object of the present invention is to provide for theincorporation of microbiocidally effective phosphate derivatives intosynthetic fibers or fabrics to provide a selfsanitizing fiber or fabricproduct with microbiocidal activity against a wide variety of organisms.

Another object of the present invention is to provide for theapplication of microbiocidally effective phosphate derivatives to thesurface of both synthetic and natural fibers and fabrics to provide aself-sanitizing fiber or fabric product with microbiocidal activityagainst a wide variety of microorganisms.

Another object of the present invention is to provide phosphatederivatives which can be incorporated into conventional plastics whichcan then be molded or otherwise constructed to provide a plastic productwith insecticidal activity.

Another object of the present invention is to provide an effectiveinsecticidal phosphate derivatives which can be mixed with an aqueousdetergent solution and used to wash an animal or object to kill or repelinsects or related organisms.

Another object of the present invention is to provide a microbiocidalphosphate derivative

These and other objects, features and advantages of the presentinvention will become apparent after a review of the following detaileddescription of the disclosed embodiment and the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention relates to microbiocidal and insecticidalcompositions comprising certain derivatives of phosphates. When used inaccordance with the present invention, the phosphate derivatives arecapable of killing or inhibiting the growth of a wide variety ofmicroorganisms including fungi, yeasts, viruses, algae and bacteria.

The phosphate derivative utilized in accordance with the presentinvention inhibits the growth of the following representativeGram-negative and Gram-positive bacteria: Sarcina lutea, Staphylococcusspecies, Pseudomonas aeruginosa, Pseudomonas cepacia, Escherichia coli,Escherichia communior, Bacillus subtilis, Klebsiella species, Salmonellaspecies, Legionella pneumophilia, Enterobacter aerogenes andStreptococcus species. The phosphate derivative also inhibits the growthof the following representative fungi and yeasts: Candida albicans,Trichophyton metagrophytes, Trichophyton rubrum, Trichophytoninterdigitale and Aspergillus niger. In addition, the phosphatederivative also inactivates Herpes simplex virus. The foregoingmicroorganisms are representative of those organisms that areresponsible for infections in hospitals and other health carefacilities.

The microbiocidal additive of the present invention can be added towater or other solvents to provide a disinfectant or can be added to aconventional detergent to provide a microbiocidal cleansing agent. Thedetergents that can be used in the present invention include, but arenot limited to, linear alkyl sulfonates and alkyl benzene sulfonates.These detergents also include, but are not limited to, metal salts oflong chain fatty acids.

Such a microbiocidal cleansing agent is effective in killing orsignificantly inhibiting the growth of a wide spectrum of bothprocaryotic and eucaryotic microorganisms which may reside on surfacesto be cleaned or treated with the microbiocidal detergent. Thus, inaccordance with the present invention, it has been determined thatcertain phosphate derivatives impart fungicidal, algaecidal, viricidaland bactericidal properties to a conventional detergent.

The microbiocidal additive of the present invention can be mixed inwater at various concentrations and be used as a disinfecting agent tokill or inhibit microorganisms that may reside on that surface. Forexample, a solution of the additive of the present invention containingfrom approximately 500 to 1000 parts per million (PPM) of the phosphatederivative makes an excellent disinfectant for light duty such asmopping and cleaning of hard surfaces such as vinyl walls, floors,counters and table tops.

For more demanding microbiocidal activity such as that required for asurgical scrub, the phosphate derivative can be mixed in with aconventional detergent at a concentration of between approximately 15%and 70% by weight.

The microbiocidal cleansing agent prepared by the addition of themicrobiocidal additive of the present invention to a conventionalcleansing agent has the capacity to kill or inhibit the growth of manytypes of bacteria, fungi, viruses, yeasts and other destructive ordisease-producing microorganisms which might be on a surface. Such amicrobiocidal cleansing agent is particularly effective against bothGram-positive bacteria, such as Staphylococcus aureus, and Gram-negativebacteria, such as Pseudomonas aeruginosa.

The microbiocidal additive of the present invention can also be added toa wide variety of permanent and non-permanent coating materials. Thesecoatings include paints of various kinds, waxes, and plastic coatings.When the coating material is applied to a surface, the microbiocidaladditive in the coating material will impart microbiocidal activitiy tothe surface. The coating materials that can be used with themicrobiocidal additive of the present invention include, but are notlimited to, coatings formed from materials including the acrylate andmethacrylate polymers and copolymers; the vinyl polymers includingpolyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinylchloride-acetate, vinyl chloride-vinylidine chloride copolymers; thepolyethylene polymers including polyethylene, polyhalogenated ethylenes,polystyrene and the styrenated alkyds. Further coating materials includethermosetting as well as other thermoplastic materials. Illustrative ofsuch materials are the alkyd resins including the modified alkyds andthe terpenic and maleic alkyds, the amino resins includingurea-formaldehyde and melamine-formaldehyde; the protein plasticsincluding casein, zein, keratin, peanut and soy bean plastics; thecellulosics including cellulose acetate, cellulose nitrate, celluloseacetate butyrate, regenerated cellulose, lignocellulose, ethylcellulose, hydroxyethyl cellulose and carboxymethyl cellulose; the epoxyresins; the ethylene and fluoroethylene polymers; the furan resins; thepolyamides; the phenolics including phenol-formaldehyde phenol-furfuraland resorcinol-formaldehyde, the polyester resins including thesaturated polyesters, the unsaturated polyesters and the polyfunctionalunsaturated esters and the silicones.

The microbiocidal additive of the present invention can be mixed inaccordance with the present invention with paint or other coatings andapplied to underwater surfaces to inhibit the growth of marineorganisms, such as algae, on such coated surfaces. For example, themicrobiocidal additive of the present invention can be incorporated intopaint and painted on a boat bottom. The treated coating will inhibit thegrowth of algae and other marine organisms on the bottom of the boat.

In addition, the microbiocidal additive can be incorporated into amaterial that is to be immersed in water for long periods of time toinhibit the growth of algae on the material. An example of such a usefor the microbiocidal additive of the present invention is incorporatingthe microbiocidal additive of the present invention into fiberglass thatis to be used to mold a boat bottom.

The microbiocidal additive of the present invention can be added to acoating material at a concentration of between approximately 0.01 to 10%by weight. The preferred concentration of phosphate derivative in thecoating material is between about 0.1% and 6% by weight with anespecially preferred concentration of between approximately 0.5% and 4%by weight.

The microbiocidal additive of the present invention can be incorporatedinto plastics to impart microbiocidal activity to the plastic products.Plastics treated with the present invention can be used to make a widevariety of products such as furniture, medical items, eating utensilsand the like. There are many advantages to constructing products fromplastic materials including lower cost and the possibility of moldingthe items in a variety of different shapes. Examples of the type ofproducts contemplated include, but are not limited to, mattress covers,crib covers, bassinet covers, draw sheets, cubicle curtains, male andfemale urinals, toilet seats, bed pans, bed pan liners, wash basins,laminated sheets of melamine and phenolic plastics such as Formica™,Micarta™, and other similar decorative surfacing materials, carafes,tooth brushes, hair brushes, combs, soap holders, denture cups, rolls ofutility sheeting, catheters, drainage bags, colostomy pouches, ileostomypouches, intravenous solution bags, irrigation solution bags, bloodbags, tubing, administration sets, donor sets, fountain syringes, enemabags, contact lens holders, examination equipment covers for all classesof trade including a medical doctor, veterinarian, dentists,optometrist, ophthalmologist, and optician, moisture barrier for thebuilding trade to eliminate mold and mildew, table tops, food handlingtrays, wall paneling, hard floor covering, epoxy tiles, epoxy grout,ceramic tile grout, carpet base, shower curtains, bath mats, andtelephone caps for mouth piece and reception unit. The product in someinstances may be molded using standard plastic molding techniques. Inother instances the product may be assembled from cut or molded partsinto a finished product.

The phosphate derivative is present in the plastic material at aconcentration of between approximately 0.1 and 10% by weight. Apreferred range of phosphate derivative in the plastic material isbetween approximately 1% and 6% by weight.

The microbiocidal additive of the present invention can be appliedtopically to both natural and synthetic fibers or can be incorporateddirectly into synthetic fibers during the manufacturing process. Thefibers that can be used with the microbiocidal additive of the presentinvention include but are not limited to fibers made of wool; cotton;polyolefin fiber including polypropylene, polybutenes, polyisoprene andtheir copolymers; polyester fiber including polyethylene terephthalate;polyaramid fiber; cellulose acetate fiber; rayon fiber; nylon fiber;polystyrene fiber; vinyl phenolic fiber; vinyl acetate fiber; vinylchloride fiber; acrylic fiber; acrylonitrile fiber; and polyurethanefiber.

Fabrics can also be treated with the microbiocidal additive of thepresent invention. These fabrics include, but are not limited to, wovenfabrics made from all of the aforementioned fibers or non-woven fabrics.The non-woven fabrics can be made, for instance, by entangling fibers ina needling process, by using a thermoplastic or adhesive backing orbinder, or by fusing fibers together with heat.

The phosphate derivative can be applied to the fiber or fabric by mixingthe phosphate derivative with a liquid such as water or other solvent ordispersant and then dipping, spraying or washing the fiber or fabric inthe phosphate derivative mixture. The concentration of phosphatederivative in the water or other solvent or dispersant is between 0.01%and 30% by weight. The preferred concentration of phosphate derivativein dispersant or solvent is between 0.1% and 10% by weight. The mostpreferred concentration of phosphate derivative in dispersant or solventis between 0.5% and 6% by weight. Suitable solvents that can be used toapply the phosphate derivative include, but are not limited to, benzene,toluene, xylene, and hexane. After applying the mixture, the fiber orfabric will be coated with the phosphate derivative. Therefore, whenmicroorganisms comes into contact with the fiber or fabric, thephosphate derivative will kill or inhibit the growth of themicroorganism.

The additive of the present invention can also be homogeneouslydistributed in a solvated fiber dope or a fiber melt before the fiber isspun at a concentration of between approximately 0.01% and 10% byweight. A preferred concentration concentration of the phosphatederivative in fiber or fabric is between 0.1% and 6% by weight.

In accordance with the present invention, the phosphate derivative canbe incorporated directly into natural or synthetic rubber, includinglatex rubber, polyvinyl acetate or polyvinyl chloride backings orbinders that are applied to a fabric. It has been found that, whenproperly incorporated in accordance with the present invention, aportion of the microbiocidal additive of the present invention willslowly migrate from the fabric backing or binder onto the fibers of thefabric thereby imparting microbiocidal activity to the fabric.

Examples of the type of fiber or fabric products contemplated include,but are not limited to, surgical gauze, padding on wound dressings,mattress covers, crib covers, bassinet covers, sailboat sails, tents,draw sheets, cubicle curtains, tooth brushes, hair brushes, fabric wallcovering, fabric base, fabric shower curtains, bath mats, athleticclothing such as underclothes, shirts, socks, shorts, pants, shoes andthe like, and hospital clothing such as examination robes, physicianscoats and nurses uniforms.

The microbiocidal additive of the present invention can be used as apreservative to prevent degradation of a product due to growth ofmicroorganisms. For example, the phosphate derivative can be mixed withwater or oil and sprayed on wood to preserve the wood against breakdowndue to microorganisms. Small amounts of the derivative can be added toinks to prevent the growth of microorganisms which will clog ink jets.The derivative can be added to cutting oils to prolong the useful lifeof the oil. The additive is also useful in inhibiting growth ofmicroorganisms in fuel and thereby decreasing the likelihood of cloggedfuel jets.

In accordance with the present invention, the phosphate derivative canbe added to the water in cooling towers or can be included in a coatingthat is used to coat the surfaces in cooling towers to kill or inhibitthe growth of the pathogen that causes Legionaire's disease, Legionellapneumophilia.

The microbiocidal additive of the present invention can be used to coatair and other filter material and media thereby killing or reducing thegrowth of microorganisms in filters. The filter material can beparticulate or can be fibrous in composition. When fluids pass throughthe filter and microorganisms are deposited upon the filter material orexposed to the filter material, the microbiocidal additive of thepresent invention will inhibit or kill the organism.

The phosphate additives can also be added in accordance with the presentinvention to various grouts, cements and concretes to impartmicrobiocidal activity to the material. For example, between about 0.01and 10% of the microbiocidal compound of the present invention can beadded to tile grout before application to a surface. The preferredconcentration of the microbiocidal additive in grout, cement or concreteis between 0.1% and 6%. The present invention will prevent unsightlymold or mildew from growing in or on the grout, concrete, or cementmaterial.

The microbiocidal phosphate additive has also been found to be aneffective insecticidal agent and an insect repelling agent. When insectssuch as flies or fleas come into contact with a product treated with themicrobiocidal additive of the present invention, the insects are killedor repelled. The insecticidal alkyl phosphate derivative, when used inaccordance with the present invention, can be utilized as an aqueousmixture or can be incorporated into a number of materials such asplastics and the like.

When the phosphate derivative is mixed with water, it can be applieddirectly to a surface to impart insecticidal and insect repellantqualities to the surface. In addition, the insecticidal alkyl phosphatederivative of the present invention can be mixed with an aqueousdetergent and used to wash objects or animals. For example, an aqueousdetergent with the alkyl phosphate derivative makes an excellent soapfor washing dogs and cats. The treated detergent kills any fleas thatmay be on the dog or cat and will repel any new fleas for a long periodof time. The phosphate derivative of the present invention is not toxicto the dog or cat.

The phosphate derivative has also been found to be an effectivedeodorant.

Although not wanting to be bound by the following description of themechanism of the microbiocidal additive of the present invention, it isbelieved that at least one free hydroxyl group on the phosphate group isnecessary for Gram negative microbiocidal activity. Thus, if all of thehydroxyl groups are replaced with alkyl or other organic groups, thephosphate derivative will no longer exhibit microbiocidal activity. Itis believed that, in general, the more hydroxyl groups that are free,the greater the microbiocidal activity will be exhibited by thephosphate derivative.

Thus the microbiocidal additive of the present invention can bedescribed as an alkyl phosphate ester having least one free hydroxylgroup. A "free hydroxyl group" is defined herein as "--OH".

The microbiocidal additive of the present invention can be morespecifically defined as a phosphate ester with at least one freehydroxyl group with the following general formula: ##STR2## wherein:

R may be alkyl, aryl, aralkyl and alkaryl groups including, but notlimited to, straight chain, branched chain or cyclic alkyl groups havingfrom 1 to 24 carbon atoms, polyoxyethylene or polyoxypropylene havingfrom 2 to 32 ethylene oxide or propylene oxide units respectively, alkylphenoxy polyoxyethylene containing 2 to 32 ethylene oxide units, alkylphenoxy polyoxyethylene containing ethylene oxide units and 1 to 24carbon atoms in the phenolic alkyl chain, and polyhydroxy compounds,including but not limited to, ethylene glycol, glycerol, or sorbitol.

R may also be hydrogen, but only if X is a quaternary amine.

X is selected from the group consisting of Group IA metals, Group IIAmetals, transition metals, hydrogen, and an organic ion. The positivelycharged ion is not necessary for microbiocidal activity.

A preferred structure of the phosphate derivative comprises thefollowing formula: ##STR3## wherein:

R=an alkyl group of from 6 to 18 carbon atoms.

X is selected from the group consisting of Group IA metals, Group IIAmetals, transition metals, hydrogen, and an organic ion. Themicrobiocidal additive defined by this formula is water insoluble oronly slightly soluble in water and is especially useful for addition tonon-aqueous products such as plastics, fibers and non-aqueous coatings.An aqueous suspension of the phosphates with the alkyl group of greaterthan 6 carbon atoms in the R position can be prepared by adding asurfactant such as Tween 80 (Sigma Chemical Company, St. Louis, MO) orother suitable nonionic surfactant.

An especially preferred structure of the microbiocidal additive of thepresent invention comprises a phosphate with the following formula:##STR4## wherein:

R=an alkyl group of from 1 to 5 carbon atoms.

X is selected from the group consisting of Group IA metals, Group IIAmetals, transition metals, hydrogen, and an organic ion.

The microbiocidal additive defined by this formula is water soluble andis especially useful as an additive for a disinfectant or for adetergent.

An additional preferred structure of the microbiocidal additive of thepresent invention has the following formula: ##STR5## wherein: X isselected from the group consisting of Group IA metals, Group IIA metals,transition metals, hydrogen, and an organic ion.

Another especially preferred embodiment of the present invention has thefollowing formula: ##STR6## wherein: X is selected from the groupconsisting of Group IA metals, Group IIA metals, transition metals,hydrogen, and an organic ion.

This embodiment of the microbiocidal additive of the present inventionis soluble in water.

When the additive utilized in accordance with the present invention isincorporated into a non-aqueous material such as a plastic or fiber, themicrobiocidal activity of the product can be improved by substitutingfor "X" a large organic ion such as a quaternary amine. An example ofsuch a compound is a tertiary amine with the following general formula:##STR7## wherein:

R₁ =an alkyl group of from 1 to 18 carbon atoms or a hydroxy alkyl groupof from 1 to 18 carbon atoms. The R₁ groups are not necessarilyidentical.

R₂ =an alkyl group of from 8 to 18 carbon atoms.

Another especially preferred embodiment of the present invention is analkyl phosphate derivative with the following formula: ##STR8##

This especially preferred embodiment can be prepared by neutralizingphosphoric acid with between 1 to 2 moles of the tertiary amine. If moretertiary amine is used to neutralize the phosphoric acid, the freehydroxyls on the phosphate group will be eliminated and it is believedthat the gram negative microbiocidal activity of the compound will bediminished.

The type of component to be used as the "X" substituent will dependlargely upon the compatibility of the base material for the "X"substituent.

The microbiocidal additive of the present invention may be prepared asfollows: One mole of phosphorous pentoxide is reacted with betweenapproximately 1 to 3 moles of an alcohol. The alcohol can be an alkyl oran aryl compound. The alkyl alcohol can be straight chained, branchedchain or cyclic. The alcohol should be heated to a temperature ofbetween approximately 60° and 120° C. depending upon the boiling pointof the alcohol used.

The phosphorous pentoxide is slowly added to the alcohol while themixture is vigorously agitated. The reaction is complete two to fourhours after the addition of phosphorous pentoxide is completed.

The product formed in this reaction is a mixture of mono-ester phosphateand di-ester phosphate. The reaction equation is as follows: ##STR9##where R is the alkyl or aryl group depending upon the substituent used.It is to be understood that the mono-ester reaction product is the mostmicrobiocidally active compound. It is believed that this is because themono-ester has a free hydroxyl group. The di-ester reaction product iseither not microbiocidally active or is only slightly microbiocidallyactive.

The phosphate derivative is an effective microbiocidal compound and iscapable of killing or inhibiting a wide variety of microorganismsincluding bacteria, yeasts, fungi, algae, molds and viruses.

The microbiocidal additive of the present invention can be modified togive the phosphate derivative physical properties which are particularlyadvantageous to the medium in which the phosphate derivative is to beused. For example, if it is desired to impart microbiocidal activity toa plastic material, it would be advantageous to have the phosphatederivative diffuse from the body of the plastic to the surface of theplastic where most of the microorganisms reside. To obtain a phosphatederivative that is capable of diffusing through a non-aqueous material,such as a fiber or plastic, to the surface of the material, thephosphate can be partially neutralized with a tertiary amine as shown inthe following reaction equation: ##STR10##

The preferable range for X is between approximately 1 and 1.5 moles withthe especially preferable range of 1.3 moles.

This reaction results in a mixture of the following mono-alkyl phosphateamine product: ##STR11## and the following di-alkyl phosphate amineproduct: ##STR12## and the following monoalkyl phosphate: ##STR13##wherein:

R=a straight chain or a branched chain alkyl group of from 1 to 18carbon atoms;

R₁ =an alkyl group of from 1 to 18 carbon atoms or a hydroxy alkyl groupof from 1 to 18 carbon atoms.

R₂ =a straight chain or a branched chain alkyl group of from 8 to 18carbon atoms.

Consistent with the proposed theory that the microbiocidal phosphatederivative requires at least one free hydroxyl, the di-alkyl phosphateamine has little microbiocidal activity. The mono-alkyl phosphate andthe mono-alkyl phosphate amine both have microbiocidal activity.

To obtain a diffusable microbiocidal additive, the above reaction iscarried out in the following manner: Between approximately 0.5 and 1.5moles of the tertiary amine per mole of the mixed phosphodiesters fromthe first reaction is slowly added to the mixture. This reaction iscarried out at a temperature of between approximately 80° C. and 120° C.depending on the phosphate used. The most preferred tertiary amine isbis(hydroxyethyl) cocoamine. The preferred phosphate derivative that iscapable of diffusing in a plastic material has the following formula:##STR14##

Although a tertiary amine with a long chain alkyl group is used in thisembodiment to promote diffusion of the phosphate derivative of thepresent invention, it is to be understood that other tertiary aminescould be used to promote diffusion. In addition, it should be noted thatwhen 1 to 1.5 moles of tertiary amine are used to partially neutralizethe alkyl phosphates, some alkyl phosphate monoester will be present inthe solution.

The microbiocidal activity of the phosphate derivative of the presentinvention is evaluated as follows. Petri dishes are prepared usingappropriate nutrient agar as a food source for the microorganism to betested. The microorganism is seeded into the agar as is well known toone of ordinary skill in the art. A hole 6 mm in diameter and 5 mm deepis cut into the agar. 0.05 ml. of each of the indicated test compoundsis placed in the hole and the inoculated petri dish is incubated for 24hours at 37° C. After the 24 hour incubation period, the relativesusceptibility of the test organisms to the phosphate derivative of thepresent invention is demonstrated by a clear zone of growth inhibitionaround the test solution. This zone of inhibition is the result of twoprocesses: (1) the diffusion of the compound and (2) growth of thebacteria. As the phosphate derivative diffuses through the agar mediumfrom the hole, its concentration progressively diminishes to a pointwhere it is no longer inhibitory for the test organism. The area of thesuppressed microbial growth, the zone of inhibition, is determined bythe concentration of the phosphate derivative present in the area.Therefore, within the limitations of the test, the area of theinhibition zone is proportional to the relative susceptibility of themicroorganisms to the phosphate derivative of the present invention.

After the 24 hour incubation period, each plate is examined and thediameters of the complete inhibition zones are noted and measured usingeither reflected light and a measuring device such as sliding calipers,a ruler, or a template prepared for this purpose and held on the bottomof the plate. The end point, measured to the nearest millimeter, is thepoint at which no visible growth that can be detected with the unaidedeye minus the diameter of the test drop or sample. The area of the zoneof inhibition is then calculated.

The following examples will serve to further illustrate the presentinvention without, at the same time, however, constituting anylimitation thereof.

EXAMPLE I

The mono-ethyl alkyl phosphate derivative is prepared as follows: Onemole of phosphorous pentoxide is reacted with three moles of ethanol ata temperature of 60° C. The phosphorous pentoxide is slowly added to theethanol while the mixture is vigorously agitated. At the reactiontemperature of 60° C. the reaction is complete in about two hours. Theprogress of the reaction is determined by titrating the acid that isproduced with a solution of potassium hydroxide. The reaction productsinclude approximately equimolar quantities of the mono-ethyl alkylphosphate and the di-ethyl alkyl phosphate. The mono-ethyl alkylphosphate is the more microbiocidally active species.

EXAMPLE II

The mono-(2-ethylhexyl) phosphate derivative is prepared as follows. Onemole of phosphorous pentoxide is reacted with three moles of2-ethylhexanol at a temperature of 100° C. The phosphorous pentoxide isslowly added to the alcohol while the mixture is vigorously agitated. Atthe reaction temperature of 100° C. the reaction is complete in abouttwo hours. The progress of the reaction is determined by titrating theacid that is produced with a solution of potassium hydroxide. Thereaction products include approximately equimolar quantities of themono-(2-ethylhexyl) alkyl phosphate and the di(2-ethylhexyl) alkylphosphate. The mono-(2-ethylhexyl) alkyl phosphate is the moremicrobiocidally active species.

EXAMPLE III

Since the preferred method of preparing the phosphate of Examples I andII results in two reaction products, the monoalkyl phosphate and thedi-alkyl phosphate, the relative microbiocidal activity of each of theproducts is evaluated.

Three samples are tested:

1. 91% mono-(2-ethylhexyl) phosphate, 9% di-(2-ethylhexyl)phosphate

2. 55% mono-(2-ethylhexyl)phosphate and 45% di-(2-ethylhexyl)phosphate

3. 95% di-(2-ethylhexyl)phosphate, 5% mono-(2-ethylhexyl)phosphate.

Petri dishes are prepared using trypticase soy nutrient agar (BaltimoreBiological Laboratory, Cockeysville, MD). The microorganisms used inthis test are the Gram-positive Staphylococcus aureus and theGram-negative Pseudomonas aeruginosa. Each microorganism is seeded intothe agar as is well known to one of ordinary skill in the art. A hole 6mm in diameter and 5 mm deep is cut into the agar. 0.05 ml. of each ofthe indicated test compounds is placed in the hole, and the inoculatedpetri dish is incubated for 24 hours at 37° C. After the 24 hourincubation period, the relative susceptibility of the test organisms tothe phosphate derivative of the present invention is demonstrated by aclear zone of growth inhibition around the test solution.

After the 24 hour incubation period, each plate is examined and thediameters of the complete inhibition zones are noted and measured asdescribed above. Each test is performed at least 6 times. The areasshown in Table A are the average of the 6 separate tests.

                  TABLE A                                                         ______________________________________                                               Zone of Inhibition in mm.sup.2                                                  91%        Mixture      95%                                                   Mono-ester 55% Mono-ester/                                                                            Diester                                      Organism 9% Di-ester                                                                              45% Di-ester 5% Mono-ester                                ______________________________________                                        S. aureus                                                                              352        240          148                                          P. aeruginosa                                                                          319        148           28                                          ______________________________________                                    

The results of Table A indicate that the mono-alkyl phosphate is thecompound which has the significant amount of the microbiocidal activity.

EXAMPLE IV

To produce a microbiocidal alkyl phosphate amine that can be used with adetergent to make a microbiocidal detergent, approximately one mole eachof the reaction products of Example II are partially neutralized with1.3 moles of bis(hydroxyethyl) cocoamine. 1.3 moles of bis(hydroxyethyl)cocoamine is slowly added to the reaction products of Example II untilthe pH is between approximately 3.2 and 3.8 in 75% ethanol. Thisreaction is carried out at a temperature of 100° C. The reaction mixtureis vigorously agitated during the reaction.

An aqueous mixture of the microbiocidal alkyl phosphate is prepared bymixing the alkyl phosphate derivative from Example II with an aqueousdetergent solution. The concentration of alkyl phosphate derivative is0.05%. The microbiocidal detergent is heated to 85° C. Cotton fabric isthen introduced and remains in the heated solution for 15 minutes. Thefabric is then rinsed in water at 40° C., removed, and dried.

Square samples of the treated fabric of approximately 400 mm² are cutand placed on agar plates which have previously been inoculated withStaphylococcus aureus and Pseudomonas aeruginosa the plates are thenincubated at 35° C. for 24 hours.

After the 24 hour incubation, neither Staphyococcus aureus norPseudomonas aeruginosa are found to be present in or on the squares.Microscopic examination shows a zone of inhibition around the individualthreads.

EXAMPLE V

To produce a microbiocidal alkyl phosphate derivative that can be usedwith a detergent to make a microbiocidal detergent, the reaction productof Example II is neutralized with bis(hydroxyethyl) cocoamine. 1.3 Molesof bis(hydroxyethyl) cocoamine per mole of the reaction product fromExample I is slowly added to the reaction product from Example II untilthe pH is between approximately 3.2 and 3.8 in a 75% ethanol solution.

EXAMPLE VI

To produce a microbiocidal alkyl phosphate derivative that is capable ofmigrating from the interior of a synthetic fiber, fabric or plastic tothe surface, the reaction product of Example II is partially neutralizedwith bis(hydroxyethyl) cocoamine. 1.3 moles of bis(hydroxyethyl)cocoamine per mole of the reaction product from Example II is slowlyadded to the reaction product from Example II until the pH is betweenapproximately 3.2 and 3.8 in a 75% ethanol solution. This reaction iscarried out at a temperature of 100° C. The reaction mixture isvigorously agitated during the reaction.

The resulting product is only slightly soluble in water and is suitablefor incorporation into synthetic fibers and plastics as they are beingformed or for topical application in an organic solvent such as ethylalcohol, benzene or xylene.

EXAMPLE VII

The microbiocidal capability of an alkyl phosphate amine is demonstratedby the following example. Between 0.5 moles and 3.0 moles ofbis(hydroxyethyl) cocoamine per mole of the reaction product fromExample II until the pH of the solution is b reaction product fromExample II until the pH of the solution is between approximately 2.5 and6 in a 75% ethanol solution. This reaction is carried out at atemperature of 100° C. The reaction mixture is vigorously agitatedduring the reaction. The resulting compounds are tested formicrobiocidal activity.

Petri dishes are prepared using trypticase soy nutrient agar (BaltimoreBiological Laboratory, Cockeysville, MD). The microorganisms used inthis test are the Gram-positive Staphylococcus aureus and theGram-negative Pseudomonas aeruginosa. The microorganisms are seeded intonutrient agar as is well known to one of ordinary skill in the art. Ahole 6 mm in diameter and 5 mm deep is cut into the agar. 0.05 ml. ofeach of the indicated test compounds is placed in the hole and theinoculated petri dish is incubated for 24 hours at 37° C. After the 24hour incubation period, the relative susceptibility of the testorganisms to the phosphate derivative of the present invention isdemonstrated by a clear zone of growth inhibition around the testsolution.

After the 24 hour incubation period, each plate is examined and thediameters of the complete inhibition zones are noted and measured.

The results are summarized in Table C.

                  TABLE C                                                         ______________________________________                                        Molar Ratio    S. Aureus    P. aeruginosa                                     of reactants   Area of Inhibition                                                                         measured in mm.sup.2                              ______________________________________                                        A.  Product of Example II                                                                        3848         706                                           B.  0.5 moles cocoamine.sup.a                                                                    1520         614                                           C.  1.0 moles cocoamine.sup.a                                                                    907          706                                           D.  1.3 moles cocoamine.sup.a                                                                    452          1257                                          E.  1.5 moles cocoamine.sup.a                                                                    452          38                                            F.  2.0 moles cocoamine.sup.a                                                                    452          13                                            G.  2.5 moles cocoamine.sup.a                                                                    201          13                                            H.  3.0 moles cocoamine.sup.a                                                                    153           0                                            I.  Cocoamine only 153           0                                            ______________________________________                                         .sup.a Moles of cocoamine reacted with one mole of the produce from           Example II.                                                              

As can be seen in Table C, sample A, which is the reaction product fromExample II, has excellent microbiocidal activity against both the Grampositive Staphylococcus aureus and the Gram negative Pseudomonasaeruginosa. The reaction product from Example II retains itsmicrobiocidal activity against both these organisms even when reactedwith up to 2 moles of the bis-hydroxyethyl cocoamine. When one mole eachof the reaction product from Example II is reacted with more than 2moles of the cocoamine, the microbiocidal activity is diminished.Although not wanting to be bound to the following mechanism, it isthought that the reduction in microbiocidal activity above 2 moles ofthe cocoamine is due to the neutralization of the free hydroxyl group onthe phosphate group. Three moles of cocoamine would theoreticallyneutralize all of the hydroxyl groups on the phosphate group andtherefore eliminate the microbiocidal activity. The cocoamine itself hasslight microbiocidal activity against the Gram positive Staphylococcusaureus. Thus, by partially neutralizing the 2-ethyhexyl phosphate withthe bis-hydroxyethyl cocoamine, the antimicrobial activity of the thephosphate is retained, and the compound now has the capability ofdiffusing from the interior to the surface of a synthetic fiber or aplastic material.

EXAMPLE VIII

The alkyl phosphate derivative from Table C, Line D of Example VII isadded to a tumble-mixing machine containing polyethylene pellets so thatthe final concentration of alkyl amine phosphate derivative is 2% byweight. The thermoplastic pellets are tumble mixed until the alkylphosphate derivative of the present invention is thoroughly distributed.After the sanitizing additive is mixed with and coated on the pelletizedplastic material, the mixture is charged to a hopper of a conventionalmelt extruder where the mixture is melted and the sanitizing additive ishomogeneously distributed throughout the melted mass by the action ofthe extruder. The resultant molten mass of plastic material is passedthrough a conventional spinneret to generate thermoplastic fiberscontaining the alkyl phosphate derivative.

EXAMPLE IX

The phosphate derivative from Table C, Line D of Example VII is added toa tumble-mixing machine containing polyethylene terephthalate polyesterpellets so that the final concentration of phosphate derivative is 2% byweight. The thermoplastic pellets are tumble mixed until the alkylphosphate derivative of the present invention is thoroughly distributed.After sanitizing additive is mixed with and coated the pelletizedplastic material, the mixture is charged to a hopper of a conventionalmelt extruder where the mixture is melted and the sanitizing additive ishomogeneously distributed throughout the melted mass by the action ofthe extruder as is well known to one of ordinary skill of the art. Theresultant molten mass of plastic material is passed through aconventional spinneret to generate polyester fibers containing the alkylphosphate derivative.

EXAMPLE X

The alkyl phosphate amine derivative from Table C, Line D of Example VIIis used to prepare a self-sanitizing plastic material in accordance withthe present invention. 1.0 part of the compound prepared in Example VIIis added to one hundred parts of polyethylene pellets. The pellets arecoated with the oily additive by tumbling the mixture for twentyminutes. The pellets so treated are then fused in a test tube byimmersing the test tube in an oil bath at 200° C. for twenty minutes.The test tube is then removed from the oil bath and allowed to cool toroom temperature whereupon the molten mass solidifies. The cooled massis then removed from the test tube and sawed into discs approximately 2mm thick and 10 mm in diameter. No degradation or other unusualcharacteristics of the polyethylene discs is noted. The discs are placedin appropriately inoculated petri dishes containing nutrient agar. Theagar is inoculated with various organisms and is allowed to incubate for24 hours at 37° C. After the incubation period, the zone of inhibitionaround the discs is measured as previously described. The results arepresented in Table D.

                  TABLE D                                                         ______________________________________                                                                      Area of                                                                       Inhibition                                      Organism        Type of Organism                                                                            in mm.sup.2                                     ______________________________________                                        Staphylococcus aureus                                                                         Gram-pos. bacteria                                                                          314                                             Pseudomonas aeruginosa                                                                        Gram-neg. bacteria                                                                           50                                             Escherichia coli                                                                              Gram-neg. bacteria                                                                          113                                             Klebsiella species                                                                            Gram-neg. bacteria                                                                          201                                             Candida albicans                                                                              Yeast         314                                             Salmonella chloerasuis                                                                        Gram-neg. bacteria                                                                          153                                             Aspergillus niger                                                                             Fungus        314                                             Tricophyton mentagrophyte                                                                     Fungus        707                                             ______________________________________                                    

As can be seen in Table D, the test demonstrates significantbactericidal activity against both Gram negative and Gram positiveorganisms as well as against representative yeasts and fungi.

EXAMPLE XI

An epoxy resin using the alkyl phosphate derivative is formualted asfollows:

    ______________________________________                                        Epoxy resin   88.2% by weight                                                 TIO2          9.8% by weight                                                  Alkyl phosphate                                                                             2.0% by weight from Example VII                                               Table C, Line D                                                 ______________________________________                                    

The epoxy resin used in this example is referred to as DGEPPA ordiglycidyl ether of bisphenol-A (Dow Chemical Company, Midland, MI).Other epoxy resins that can be used with the present invention areepichlorohydrin/bisphenol-A, glycidated novolacs, epoxylated novolacs,and cycloaliphatic epoxy resins.

After thoroughly mixing the above ingredients, the resin system isallowed to react with a stoichiometric amount of hardener (cross linkingreagent). Before the cross-linking reaction is completed, samples of heself-sanitizing epoxy are poured into 100×15 mm test tubes. Uponcompletion of the hardening reaction, the epoxy sample is a hardcylinder measuring 60 mm long and 15 mm in diameter and weighingapproximately 28.89 grams. Samples are cut in the form of discs with asurface area of 176.63 mm². The cut samples are placed in petri dishescontaining nutrient agar (Trypticase Soy Nutrient Agar, BaltimoreBiological Laboratory, Cockeysville, MD) inoculated with a lawn of theindicated microorganisms. It is found, upon incubation of the dishesthat the epoxy disc inhibits the growth of bacteria and fungi around thespecimen and creates a zone of inhibition. The results of the test aresummarized in Table E.

                  TABLE E                                                         ______________________________________                                                                     Area                                                                          of Inhibition                                    Organism       Type of Organism                                                                            in mm.sup.2                                      ______________________________________                                        Staphylococcus aureus                                                                        Gram-pos. bacteria                                                                          314                                              Pseudomonas aeruginosa                                                                       Gram-neg. bacteria                                                                           28                                              Escherichia coli                                                                             Gram-neg. bacteria                                                                          380                                              Klebsiella species                                                                           Gram-neg. bacteria                                                                          380                                              Candida albicans                                                                             Yeast         153                                              Salmonella cholerasuis                                                                       Gran-neg. bacteria                                                                          452                                              Aspergillus niger                                                                            Fungus         28                                              Tricophyton mentagrophyte                                                                    Fungus         50                                              Bacillus megaterium                                                                          Gram-pos. bacteria                                                                           13                                              ______________________________________                                    

As shown in Table E, the alkyl phosphate derivative, when added to epoxyresins, is effective in killing a wide variety of species ofmicroorganisms.

EXAMPLE XII

The insecticidal activity of the alkyl phosphate derivative is shown inthis Example. The minimum dose to kill 100% of a population of crickets(Acheta domesticus) is first determined. A test chamber is prepared fortesting each concentration of the alkyl phosphate amine derivative fromTable C, Line D of Example VII. The test chambers are constructed asfollows: Plastic petri dish bottoms are secured to a piece of plywood.Five crickets are placed into each dish. A piece of wire window screenis placed over each dish. Each dish was sprayed with approximately 0.5ml of a solution of the alkyl phosphate derivative from Example II. Thealkyl phosphate amine was mixed with water. The concentrations of thealkyl phosphate amine that are tested are as follows: 0.08%, 0.12%,0.16%, and 0.2%. The results of the test are summarized in Table F.

                  TABLE F                                                         ______________________________________                                                       Time of                                                        Sample         observation    Results                                         ______________________________________                                        Control        5     min.     all 5 insects alive                                            30    min      all 5 insects alive                                            24    hours    all 5 insects alive                             0.08% Alkyl Phosphate                                                                        5     min      2 alive, 3 dead                                                30    min      2 alive, 3 dead                                                24    hours    2 alive, 3 dead                                 0.12% Alkyl Phosphate                                                                        5     min      4 alive, 1 dead                                                30    min      4 alive, 1 dead                                                24    hours    2 alive, 3 dead                                 0.16% Alkyl Phosphate                                                                        5     min      2 alive, 3 dead                                                30    min      2 alive, 3 dead                                                24    hours    1 alive, 4 dead                                 0.2% Alkyl Phosphate                                                                         5     min      1 alive (weak), 4 dead                                         30    min      1 alive (weak), 4 dead                                         24    hours    all five dead                                   ______________________________________                                    

The mechanism of insecticidal activity appears to be different than thatof the microbiocidal activity. The phosphate derivative without thequaternary amine group has no insecticidal activity and the quaternaryamine group by itself will not kill the insects tested.

EXAMPLE XIII

The insecticidal activity of the alkyl phosphate amine derivative fromTable C, Line D of Example VII that was distributed in a polyethylenesheet is tested. A polyethylene film is prepared by adding 90.72 gramsof the alkyl phosphate derivative prepared in Example II to 52.5 poundsof polyethylene resin pellets and tumbling the mixture until the alkylphosphate derivative is homogeneously distributed in the pellet mixture.The treated polyethylene pellets are then extruded in a commercialextruder to form a polyethylene film that has a thickness ofapproximately 4 mils. A control film is extruded with polyethylene thatdoes not contain any alkyl phosphate derivative.

Circular test samples of both the alkyl phosphate derivative treatedpolyethylene film and control polyethylene film are cut to fit thebottom of a 15×100 mm petri dish. The circular test samples containingthe alkyl phosphate derivative are placed in the bottom of petri dishesand the circular test samples that do not contain alkyl phosphatederivative are placed in the bottom of separate petri dishes. Fourinsects are used to test the insecticidal activity of the alkylphosphate derivative as follows: cockroaches, ticks, houseflies, andfleas. The insects are placed in individual petri dishes with either thetreated polyethylene film or the control polyethylene film and observed.The time that the insect dies is noted for both alkyl phosphate treatedpolyethylene film and untreated polyethylene film. The results of thetest are shown in Table G.

                  TABLE G                                                         ______________________________________                                        Test Film   Roach   Tick      Fly   Flea                                      ______________________________________                                        Phosphate   30 min  8 hours   8 hours                                                                             30 min                                    Treated Film                                                                  Control Film                                                                              Alive after 8 hours                                               ______________________________________                                    

There is no noticeable impairment of the insects that were placed in thepetri dishes with the untreated polyethylene film after 8 hours.

EXAMPLE XIV

In this example, the alkyl phosphate derivative from Table D, Line D ofExample VII is used to prepare a self-sanitizing vinyl product inaccordance with the present invention. A polyvinyl chloride (PVC) systemusing the microbiocidal additive of the present invention is formulatedas follows:

    ______________________________________                                        Test Sample                                                                   ______________________________________                                        100        Grams of polyvinyl chloride                                        55         Grams of diotylphthalate (plasticizer)                             1.5        Grams Stabilizer                                                   9.0        Grams TiO.sub.2                                                    1.0        Grams Color concentrate                                            3.5        Grams alkyl phosphate from Table D,                                           Line D of Example VIII                                             ______________________________________                                        Control                                                                       ______________________________________                                        100        Grams of polyvinly chloride                                        55         Grams of dioctylphthalate (plasticizer)                            1.5        Grams Stabilizer                                                   9.0        Grams TiO2                                                         1.0        Grams Color concentrate                                            ______________________________________                                    

The above samples are then poured on glass plates to a thickness ofapproximately 0.25 cm and cured in an oven at a temperature ofapproximately 325° F. After the sample has polymerized, test specimensfrom each formulation are cut into circles approximately 2 cm across.

Two test organisms are seeded on two separate petri dishes of agar. Onedish is seeded with Staphylococcus aureus at a concentration of greaterthan 10³ organisms per ml. The second dish is seeded with Pseudomonascepacia at a concentration of greater than 10³ organisms per ml.

One plug each of the test vinyl sample with the alkyl phosphate aminederivative added and the control vinyl sample with no alkyl phosphateare placed onto the surface of the agar in each inoculated petri dish.The dishes are incubated in a humidified incubation chamber at atemperature of approximately 37° C. for 24 hours. At the end of the 24hour incubation period, the dishes are removed from the incubator andthe area of clear zone of inhibition around the test samples ismeasured. The clear zone of inhibition around the samples representsinhibition of growth of bacteria due to the diffusion of antimicrobialalkyl phosphate from the vinyl plug. The results of the test are shownin Table H.

                  TABLE H                                                         ______________________________________                                                 Test Organism                                                                 Zone of inhibition in mm.sup.2                                       Sample    Staphylococcus aureus                                                                          Pseudomnas cepacia                                 ______________________________________                                        Test vinyl                                                                              50               50                                                 Control    0                0                                                 ______________________________________                                    

As can be seen in Table H, the test demonstrates significantbactericidal activity against both Gram negative and Gram positiveorganisms.

EXAMPLE XV

In this example, the alkyl amine phosphate derivative from Table C, LineD of Example VII is used to produce a microbiocidal fiber. The phosphatederivative from Table C, Line D, of Example VII is melt spun with fourpolymers at a concentration of 1-2% by weight. The polymers that areused in this example are polypropylene, polyethylene, nylon andpolyester.

Polyethylene with and without the alkyl phosphate amine and thepolyester with the additive gave poor spinning performance and did notproduce a satisfactory package of spun yarn. The other fibers producedare drawn at about 3/1 draw ratio and tested for tensile properties. Theproperties appear adequate for normal apparel type textile fibers beingin the range of 3-4 grams force per denier and 20 to 40% elongation atthe brake point. The addition of the microbiocidal additive or thepresent invention causes a small to moderate decrease in both tenacityand breaking elongation, but still produces fibers with adequate tensileproperties for textile applications.

Polypropylene is extruded with few if any problems. The extrusiontemperature is set at approximately 200° C. for zone 1 and about 225° C.for the other three zones. A small amount of Carbowax (1500) is dilutedin water to about 20% and is used as a spin finish. The spin finish isselected because it is not likely to affect the results of antibacterialtesting and because the material will wash off in water. Drawing of thepolypropylene is done cold at about 3/1 draw ratio on a four roll drawwinding stand designed by Bouligny. At least five tensile tests are runon each sample. Denier is determined from the weight of a 90 cm sample(weight measured to the nearest 0.1 mg) on an analytical balance. Thestrain rate is 100% per minute on a five inch sample.

    ______________________________________                                        Properties of Polyethylene Yarn                                                              Polypropylene                                                                             Polypropylene                                      Physical Properties                                                                          Control     with additive                                      ______________________________________                                        denier (g/9000 M)                                                                            179         174                                                tenacity (g/denier)                                                                          4.15        3.95                                               breaking elongation (%)                                                                      30.4        23.3                                               ______________________________________                                    

Nylon is successfully extruded at a temperature of 260° C. in zone 1 and280° C. to 290° C. in the other zones. The spin finish is Carbowax inwater. Samples are drawn at slightly less than 3/1 draw ratio with a toproll temperature of 50° C.

Polyester is spun under conditions similar to nylon. When themicrobiocidal alkyl phosphate amine is added, the nylon became lightbrown and excessive dripping at the spinnerette is noted. The problemcan be reduced by reducing the concentration of the microbiocidal alkylphosphate amine in the feed chips and by optimizing the extrusiontemperature.

    ______________________________________                                        Properties of Nylon Yarn                                                                        Nylon    Nylon                                              Physical Properties                                                                             Control  with additive                                      ______________________________________                                        denier (g/9000 M) 280      251                                                tenacity (g/denier)                                                                             3.33     2.98                                               breaking elongation (%)                                                                         42.4     27.3                                               ______________________________________                                    

A polyethylene sample is extruded under conditions similar to those usedwith polypropylene. The polyethylene is a linear low density,fiber-grade polyethylene. Polyethylene fibers are collected as bothcontrol (no microbiocidal alkyl phosphate amine present) and fiber withapproximately 1.25% microbiocidal alkyl phosphate amine present.

EXAMPLE XVI

Each of the fibers that is prepared in Example XV are evaluated formicrobiocidal activity by the following procedure:

Nutrient media is prepared and divided into three portions. One portionis seeded from a twenty-four hour culture of Staphylococcus aureus. Thisorganism is representative of Gram positive bacteria. The second portionis seeded from a twenty-four hour culture of Pseudomonas aeruginosa.This bacteria is representative of the Gram negative bacteria. The thirdportion of the nutrient media is seeded from a twenty-four hour cultureof Corynebacterium diphtheriae.

The appropriate seed agar is poured into 150×50 mm sterile petri dishes(separate dishes for each bacteria). The seeded agar is allowed tosolidify. The test fibers, along with the control fibers containing noalkyl phosphate amine, are placed on the agar and incubated for 24 hoursat 37° C. After the twenty four hours incubation, the fibers areexamined using a 20 power stereomicroscope. Zones of inhibition areobserved around each fiber containing the alkyl phosphate amineindicating that the fiber is microbiocidal. No inhibition of growth isnoted on or around any of the control fibers.

EXAMPLE XVII

The algaecidal activity of the microbiocidal additive of the presentinvention was evaluated as follows:

Three samples of different polymers are suspended in a 20 gallon glassaquarium which is filled with pond water and seeded with a variety offresh water algae. An air pump is attached to the glass tank to keep theoxygen concentration in the water at a constant value. No agitation ofthe water other than that caused by the air bubbles occurs. The polymersamples remain in the aquarium for 60 days. At the end of 60 days, thesamples are removed and evaluated. Following evaluation, all samples aresubjected to flowing water from a faucet at full pressure of fortypounds about 6 inches from the faucet opening for a period of 60 sixtyseconds.

During the 60 day test period, observations are made daily and duringthe first 14-20 days the polymers varies in resistance to algaeaccumulation when compared to the controls. Controls begin accumulatingalgae within 48 hours. When the treated polymers are disturbed by therunning water, the algae is easily washed off of the sample. When thecontrol samples are exposed to the running water, the algae is notwashed off the sample. Although some algae does grow on the treatedpolymers, it is found that the algae is not securely anchored to thetreated polymer. The algae is very securely anchored to the control,untreated polymers.

While this invention has been described in detail with particularreference to preferred embodiments thereof, it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention as described hereinbefore and as defined in theappended claims.

I claim:
 1. A method for preparing a microbiocidal compositioncomprising the steps of:(a) reacting phosphorous pentoxide with 3 molesor more of a C₁ to C₂₄ hydroxy alkyl, aryl, aralkyl, or alkaryl compoundper mole of phosphorous pentoxide at a temperature of betweenapproximately 60° C. and 120° C. to form a phosphoric acid derivativewith at least one free hydroxyl group; and (b) reacting the product ofstep (a) with between approximately 0.5 and 1.5 moles of a tertiaryamine of the formula N(R₁)₂ R₂, wherein R₁ is a hydroxy alkyl group offrom 1 to 18 carbon atoms, and R₂ is an alkyl group of from 8 to 18carbon atoms.
 2. The method of claim 1, wherein the phosphorouspentoxide is reacted with a C₁ to C₁₈ hydroxy alkyl compound.
 3. Themethod of claim 2, wherein the hydroxy alkyl compound is 2-ethylhexanol.4. The method of claim 1, wherein N(R₁)₂ R₂ is N(C₂ H₄ OH)₂ (C₁₂ H₂₅)H⁺.5. The method of claim 1, further comprising adding the microbiocidalcomposition to a polymer or copolymer.
 6. The method of claim 1, furthercomprising applying the microbiocidal composition to a polymer orcopolymer.
 7. The method of claim 5, wherein the polymer comprises amonomer selected from the group consisting of acrylic acid, methacrylicacid, vinyl chloride, vinyl acetate, vinyl butyral, vinylidene chloride,ethylene, halogenated ethylene, styrene and styrenated alkyd.
 8. Themethod of claim 6, wherein the polymer comprises a monomer selected fromthe group consisting of acrylic acid, methacrylic acid, vinyl chloride,vinyl acetate, vinyl butyral, vinylidene chloride, ethylene, halogenatedethylene, styrene and styrenated alkyd.
 9. The method of claim 1,further comprising adding the microbiocidal composition to athermoplastic material.
 10. The method of claim 9, wherein thethermoplastic material is selected from the group consisting of alkydresins, amino resins, protein plastics, cellulosics, epoxy resins,ethylene and fluoroethylene polymers, furan resins, polyamides,phenolics, polyesters, polyfunctional unsaturated esters, and silicones.11. The method of claim 1, further comprising adding the microbiocidalcomposition to a material in a concentration range of 0.1 to 10% byweight.
 12. The method of claim 1, further comprising adding themicrobiocidal composition to a material in a concentration range of 0.1to 6% by weight.
 13. The method of claim 1, further comprising addingthe microbiocidal composition to a material in a concentration range of0.5 to 4% by weight.
 14. The method of claim 1, further comprisingapplying the microbiocidal composition to a fiber.
 15. The method ofclaim 14, wherein the fiber is selected from the group consisting ofwool, cotton, polyolefin, polyester, polyamide, cellulose acetate,rayon, polystyrene, vinyl phenolic, vinyl acetate, vinyl chloride,acrylic, acrylonitrile, and urethane.
 16. The method of claim 14,further comprising applying the microbiocidal composition to the fiberby dipping, spraying, or washing the fiber or fabric with themicrobiocidal composition.
 17. The method of claim 1, further comprisingincorporating the microbiocidal composition into a natural or syntheticrubber.
 18. The method of claim 1, further comprising incorporating themicrobiocidal composition into a fiber.